α-arylacrylates substituted by a heterocyclic radical, and fungicides which contain these compounds

ABSTRACT

α-Arylacrylates substituted by a heterocyclic radical and of the general formula I ##STR1## where R 1  is alkoxy or alkylthio, R 2  is alkyl, Het is pyridyl, pyridone, quinolyl, pyrimidinyl, pyrimidinone, the heterocyclic ring system being unsubstituted or substituted, A is carbonyloxy, oxygen or sulfur, and n is 0 or 1, and their plant-tolerated acid addition salts and metal complexes, and the N-oxides of the heterocyclic compounds, and fungicides containing these compounds.

This application is a division of application Ser. No. 07/376,999, filedJul. 7, 1989 now U.S. Pat. No. 5,157,037 issued Oct. 20, 1992. Thisapplication is also related to application Ser. No. 07/645,604, filedJan. 25, 1991, as a divisional of said application Ser. No. 07/376,999.

The present invention relates to useful novel α-arylacrylatessubstituted by a heterocyclic radical and having a fungicidal action,and fungicides which contain these compounds.

It is known that methyl acrylates, for example methylα-(2-benzyloxyphenyl)-β-methoxyacrylate or methylα-(2-pyrid-2-yloxyphenyl)-β-methoxyacrylate or methylα-(2-(6-methylpyrid-2-yl)-oxyphenyl)-β-methoxyacrylate or methylα-(2-phenoxymethylphenyl)-β-methoxyacrylate (EP-178 826, 242 070 and 242081) can be used as fungicides. However, their fungicidal action isunsatisfactory.

We have found that α-arylacrylates which are substituted by aheterocyclic radical and are of the general formula I ##STR2## where R¹is C₁ -C₄ -alkoxy or C₁ -C₄ -alkylthio, R² is C₁ -C₄ -alkyl, Het ispyridyl, pyrid-2-on-1-yl, pyrid-4-on-1-yl, quinolyl, pyrimidinyl,pyrimidin-2-on-1-yl, pyrimidin-4-on-1-yl or pyrimidin-6-on-1-yl, theheterocyclic ring system being unsubstituted or substituted by halogen,C₁ -C₈ -alkyl, C₃ -C₆ -cycloalkyl, C₁ - or C₂ -haloalkyl, C₁ -C₄-alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, aryl , aryl-C₁-C₄ -alkyl, C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxycarbonyl or cyano, A iscarbonyloxy, oxygen or sulfur and n is 0 or 1, and their plant-toleratedacid addition salts and metal complexes and the N-oxides of theheterocyclic compounds have an excellent fungicidal action, which isbetter than that of the known methyl acrylates.

The radicals mentioned in the general formula may have, for example, thefollowing meanings: R¹ may be, for example, C₁ -C₄ -alkoxy (for examplemethoxy, ethoxy, n-propoxy, isopropoxy or butoxy) or C₁ -C₄ -alkylthio(for example methylthio, ethylthio, n-propylthio, isopropylthio orbutylthio).

R² may be, for example, C₁ -C₄ -alkyl (for example methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl).

Het may be, for example, pyrid-2-yl, pyrid-3-yl, pyrid-4-yl,pyrid-2-on-1-yl, pyrid-4-on-1-yl, quinol-2-yl, quinol-3-yl, quinol-4-yl,quinol-8-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl,pyrimidin-2-on-1-yl, pyrimidin-4-on-1-yl or pyrimidin-6-on-1-yl, and theheterocyclic ring system may be unsubstituted or substituted by one tothree of the following radicals: halogen (for example fluorine, chlorineor bromine), C₁ -C₈ -alkyl (for example methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, tert-pentyl, or neopentyl, hexyl, heptyl oroctyl), C₃ -C₆ -cycloalkyl (for example cyclopropyl, cyclobutyl,cyclopentyl or cyclohexyl), C₁ - or C₂ -haloalkyl (for exampledifluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl or pentafluoroethyl), C₁ -C₄ -alkoxy (for examplemethoxy, ethoxy, n-propoxy, or isopropoxy, n-butoxy, isobutoxy,sec-butoxy or tert-butoxy), C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl (for examplemethoxymethyl, ethoxymethyl, methoxyethyl or propoxymethyl), aryl (forexample phenyl), aryl-C₁ --C₄ -alkyl (for example benzyl, 2-phenylethyl,3-phenylpropyl or 4 -phenylbutyl), C₁ -C₄ -alkylcarbonyl (for exampleacetyl, ethylcarbonyl, propylcarbonyl or butylcarbonyl), C₁ -C₄-alkoxycarbonyl (for example methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl or butoxycarbonyl), cyano, C₁ -C₄ -alkylthio (forexample methylthio, ethylthio, propylthio).

The radical A mentioned in the general formula I may be, for example,carbonyloxy, oxygen or sulfur.

Where n is 0, (A)_(n) is a single bond.

The compounds where n is 1 are preferred. When n is 0, the heterocyclicCO-containing radicals are bonded in the 1-position, i.e. via N, to theCH₂ group of the phenyl radical.

The novel compounds can also be converted by reaction with acids intoplant-tolerated acid addition salts of the inorganic or organic acids,for example into salts of hydrochloric acid, hydrobromic acid, nitricacid, oxalic acid, acetic acid, sulfuric acid, phosphoric acid ordodecylbenzenesulfonic acid. The activity of the salts is due to thecation, so that in general any anion may be chosen.

Furthermore, the novel compounds can be converted into metal complexesby known methods. This can be carried out by reacting these compoundswith the metal salts, for example salts of the metals copper, zinc,iron, manganese or nickel, e.g. copper(II) chloride, zinc(II) chloride,iron(III) chloride, copper(II) nitrate, manganese(II) chloride ornickel(II) bromide.

By reacting the novel compounds with oxidizing agents, for example withm-chloroperbenzoic acid, the N-oxides of the heterocyclic compounds areobtained.

The novel compounds can be prepared, for example, by the followingprocesses:

The novel compounds of the general formula Ia 25 (Het is pyridyl,quinolyl or pyrimidinyl, A is carbonyloxy, n is 1 and R¹ and R² eachhave the abovementioned meanings) are prepared, for example, by reactingan α-(2-bromomethylphenyl)-acrylate of the general formula III with analkali metal salt, alkaline earth metal salt or ammonium salt of aheterocyclic carboxylic acid IV in a solvent or diluent and with orwithout the addition of a catalyst. ##STR3##

The preparation of carboxylic esters from alkyl halides and carboxylatesis known per se (cf. for example Synthesis 1975, 805).

Examples of suitable solvents or diluents for the reaction of III withIV are acetone, acetonitrile, dimethyl sulfoxide, dioxane,dimethylformamide, N-methylpyrrolidone, N,N'-dimethylpropyleneurea andpyridine. It may also be advantageous to add a catalyst, for exampletetramethylethylenediamine or tris-(3,6-dioxaheptyl)amine, to thereaction mixture (cf. J. Org. Chem. 50 (1985), 3717).

The corresponding reactions can also be carried out in a two-phasesystem (e.g. carbon tetrachloride water). Examples of suitablephase-transfer catalysts are trioctylmethylammonium chloride andcetyltrimethylammonium chloride (cf. Synthesis 1974, 867, and J. Amer.Chem. Soc. 110 (1988), 185).

The heterocyclic carboxylates of the general formula IV can be preparedin a known manner from the corresponding carboxylic acids and bases (forexample potassium hydroxide) in an inert solvent (for example ethanol).

α-Bromomethylphenylacrylates of the general formula III are disclosed inDE-35 19 280, DE-35 45 318 and DE-35 45 319.

For the preparation of the novel compounds of the general formula Ib(where Het is pyridyl, quinolyl or pyrimidinyl, A is oxygen or sulfur, nis 1 and R¹ and R² each have the abovementioned meanings), theheterocyclic compounds of the general formula Het-AH (II) are reactedwith α-bromomethylphenylacrylates of the general formula III. ##STR4##

The novel compounds of the general formula Ic (where Het ispyrid-2-on-1-yl, pyrid-4-on-1-yl, pyrimidin-2-on-1-yl,pyrimidin-4-on-1-yl or pyrimidin-6-on-1-yl, n is 0 and R¹ and R² eachhave the abovementioned meanings) are formed in the reaction of theheterocyclic compounds of the general formula Het-OH IIa withα-bromomethylphenylacrylates of the general formula III in accordancewith the above equation.

A compound Het-OH, for example 2-hydroxypyridine, can react in twotautomeric forms ##STR5## i.e. as 2-hydroxypyridine or pyrid-2-one.

Accordingly, the reaction with the bromomethyl compound takes place at Nor at O, i.e. in the 1-position or in the 2-position. The same applies,for example, to the compound pyrid-4-one.

The end products which contain the CO group in the ring of theheterocyclic radical are bonded via N, i.e. in the 1-position, to theCH₂ group of the benzyl radical.

The compounds of the general formula Ic are structural isomers of thecorresponding compounds of the general formula Ib. The productdistribution between Ib and Ic is dependent on the substituents on theheterocyclic structure. The percentage of Ic in the total yield (Ib+Ic)may be from 0 to 100%.

The structural isomers Ib and Ic can be separated into the purecompounds in a conventional manner, for example by fractionalcrystallization or by chromatography.

The reactions to give the compounds Ib and Ic can be carried out, forexample in an inert solvent or diluent (for example acetone,acetonitrile, dimethyl sulfoxide, dioxane, dimethylformamide,N-methylpyrrolidone, N,N'-dimethylpropyleneurea or pyridine) using abase (for example sodium carbonate or potassium carbonate). It may alsobe advantageous to add a catalyst, for exampletris(3,6-dioxaheptyl)-amine, to the reaction mixture (J. Org. Chem. 50(1985), 3717) .

In an alternative procedure, it is also possible first to convert thecompounds of the general formula II into the corresponding sodium orpotassium salts with a base (for example sodium hydroxide or potassiumhydroxide), and then to react these salts in an inert solvent or diluent(for example dimethylformamide ) with the α-bromomethylphenylacrylatesIII to give the corresponding compounds of the general formula Ib or Ic.

The heterocyclic starting compounds of the general formula Het--(A)_(n)--H (where Het, n and A have the abovementioned meanings) are eitherknown or can be prepared by processes similar to the known processes.Appropriate preparation processes are described in, for example, EP 224217 , DE-25 31 035, J. Heterocyclic Chem. 20 (1983), 219, and J.Heterocyclic Chem. 24 (1987), 709.

Because of their C═C double bond, the novel compounds of the generalformula I can occur both as E isomers and as Z isomers. Both theindividual isomeric compounds and their mixtures are embraced by theinvention and can be used as fungicides. Preferably, the mixturesobtained in the synthesis are used as fungicides.

The Examples which follow illustrate the preparation of the novel activeingredients.

EXAMPLE 1 Methylα-[2-(pyrid-3'-yl)-carbonyloxymethylphenyl]-β-methoxyacrylate (compoundno. 13 ) ##STR6##

12.3 g (0.1 mole) of nicotinic acid and 5.6 g (0.1 mole) of potassiumhydroxide are dissolved in 150 ml of ethanol and the solution is stirredfor two hours at room temperature (20° C.). The white precipitate whichseparates out is filtered off under suction, washed with diethyl etherand suspended in 300 ml of dimethylformamide. Thereafter, 28.5 g (0.1mole) of methyl α-(2-bromomethylphenyl)-β-methoxyacrylate are added. Thereaction mixture is stirred for two hours at 110° C., left to cool andevaporated down, and the residue is taken up in methylene chloride. Theorganic phase is washed with water, dried over MgSO₄ and evaporateddown. The resulting oil is chromatographed over silica gel (5:1cyclohexane/ethyl acetate). 23.9 g (73%) of the title compound areobtained as a colorless, viscous oil.

EXAMPLE 2 Methyl α-[2-(pyrid-2'-yl)-thiomethylphenyl]-α-methoxyacrylate(compound no. 53) ##STR7##

11.1 g (0.1 mole) of 2-mercaptopyridine, 28.5 g (0.1 mole) of methylα-(2-bromomethylphenyl)-β-methoxyacrylate and 20.7 g (0.15 mole) ofpotassium carbonate in 250 ml of dimethylformamide are stirred for 48hours at room temperature. Thereafter, the reaction mixture isevaporated down, the residue is taken up in methylene chloride and theorganic phase is washed with water and dried over MgSO₄. The oilobtained after evaporation is filtered over silica gel (cyclohexane).14.5 g (46%) of the title compound are obtained as a colorless oil.

EXAMPLE 3 Methylα-[2-(6'-methylpyrid-2'-yl)-oxymethylphenyl]-β-methoxyacrylate (compoundno. 54 ) and methylα-[2-(6'-methylpyrid-2'-on-1'-yl)-methylphenyl]-β-methoxyacrylate(compound no. 248) ##STR8##

10.9 g (0.1 mole) of 6-methylpyrid-2-one, 28.5 g (0.1 mole) of methylα-(2-bromomethylphenyl)-β-methoxyacrylate and 20.7 g (0.15 mole) ofpotassium carbonate in 250 ml of dimethylformamide are stirred for 48hours at room temperature. Thereafter, the reaction mixture isevaporated down, the residue is taken up in methylene chloride and theorganic phase is washed with water and dried over MgSO₄. The oilobtained after evaporation is triturated with diethyl ether. 4.7 g (15%)of compound no. 248 are obtained in the form of colorless crystals. Themother liquor is evaporated down and the residue is triturated withdiisopropyl ether. 10.6 g (34%) of compound no. 54 are now obtained inthe form of colorless crystals.

EXAMPLE 4 Methylα-[2-(4'-methylquinol-2'-yl)-oxymethylphenyl]-β-methoxyacrylate(compound no. 134) ##STR9##

15.9 g (0.1 mole) of 4-methyl-2-hydroxyquinoline and 4.0 g (0.1 mole) ofNaOH are dissolved in 150 ml of ethanol and the solution is stirred for2 hours at room temperature. The precipitate which separates out isfiltered off under suction, washed with diethyl ether and suspended in400 ml of dimethylformamide. Thereafter, 28.5 g (0.1 mole) of methylα-(2-bromomethylphenyl)-β-methoxyacrylate are added. The reactionmixture is stirred for 48 hours at room temperature and evaporated down,and the residue is taken up in methylene chloride. The organic phase iswashed with water, dried over MgSO₄ and evaporated down. The resultingoil is chromatographed over silica gel (5:1 cyclohexane/ethyl acetate).13.1 g (36%) of the title compound are obtained as a colorless oil.

EXAMPLE 5 Methylα-[2-(pyrimid-4'-on-1'-yl)-methylphenyl]-β-methoxyacrylate (compound no.252) and methylα-[2-(pyrimid-6'-on-1'-yl)-methylphenyl]-β-methoxyacrylate (compound no.253) ##STR10##

9.6 g (0.1 mole) of pyrimidin-4-one, 28.5 g (0.1 mole) of methylα-(2-bromomethylphenyl)-β-methoxyacrylate and 20.7 g (0.15 mole) ofpotassium carbonate in 250 ml of dimethylformamide are stirred for 48hours at room temperature. Thereafter, the precipitate is filtered off,the filtrate is evaporated down and the residue is taken up in methylenechloride. The organic phase is washed with water, dried over MgSO₄ andevaporated down. The resulting oil is chromatographed over silica gel(20:1 methylene chloride/methanol). 6.3 g (21%) of compound no. 253 areobtained in the form of colorless crystals by trituration withdiisopropyl ether, and 6.3 g (21%) of compound no. 252 are obtained,likewise in the form of colorless crystals, by trituration with diethylether.

EXAMPLE 6 Methyl α-[2-(2',6'-bistrifluoromethylpyrimid-4'-yl)-oxymethylphenyl]-β-methoxyacrylate (compound no. 202 ) ##STR11##

23.2 g (0.1 mole) of 2,6-bistrifluoromethyl-4-hydroxypyrimidine, 28.5 g(0.1 mole) of methyl α-(2-bromomethylphenyl)-β-methoxyacrylate and 20.7g (0.15 mole) of potassium carbonate in 250 ml of dimethylformamide arestirred for 48 hours at room temperature. Thereafter, the reactionmixture is evaporated down, the residue is taken up in methylenechloride and the organic phase is washed with water and dried overMgSO₄. The oil obtained after evaporation is filtered over silica gel(cyclohexane). After the solvent has been removed, 24 g (55%) of thetitle compound is obtained in the form of colorless crystals.

The following compounds can be prepared in a similar manners:

                  TABLE 1                                                         ______________________________________                                         ##STR12##                                                                    Compounds of the formula Ia                                                   (A = carbonyloxy, R.sup.1 = OCH.sub.3, R.sup.2 = CH.sub.3)                    The configuration statement refers to the β-methoxyacrylate              group.                                                                        No.     Het                 mp. (isomer)                                      ______________________________________                                         1      2-pyridyl           oil (E)                                            2      4-methyl-2-pyridyl                                                     3      4-fluoro-2-pyridyl                                                     4      4-chloro-2-pyridyl                                                     5      6-methyl-2-pyridyl                                                     6      6-ethyl-2-pyridyl                                                      7      6-n-propyl-2-pyridyl                                                   8      6-isopropyl-2-pyridyl                                                  9      6-n-butyl-2-pyridyl                                                   10      6-chloro-2-pyridyl                                                    11      3,6-dichloro-2-pyridyl                                                12      5-n-butyl-2-pyridyl                                                   13      3-pyridyl           oil (E)                                           14      2-methyl-3-pyridyl                                                    15      2-chloro-3-pyridyl                                                    16      2-fluoro-3-pyridyl                                                    17      4-chloro-3-pyridyl                                                    18      5-fluoro-3-pyridyl                                                    19      6-chloro-3-pyridyl                                                    20      4-pyridyl                                                             21      2-methyl-4-pyridyl                                                    22      2,6-dimethyl-4-pyridyl                                                23      2,3-dimethyl-4-pyridyl                                                24      2-phenyl-3-methyl-4-pyridyl                                           25      3-methyl-4-pyridyl                                                    26      2-ethyl-4-pyridyl                                                     27      2-n-propyl-4-pyridyl                                                  28      2-n-butyl-4-pyridyl                                                   29      2-chloro-4-pyridyl                                                    30      2,6-dichloro-4-pyridyl                                                31      2-quinolyl                                                            32      3-quinolyl          105-106° C. (E)                            33      4-quinolyl                                                            34      2-methyl-4-quinolyl                                                   35      2-ethyl-4-quinolyl                                                    36      2-n-propyl-4-quinolyl                                                 37      2-isopropyl-4-quinolyl                                                38      2-tert-butyl-4-quinolyl                                               39      2-cyclohexyl-4-quinolyl                                               40      3-methyl-4-quinolyl                                                   41      3-ethyl-4-quinolyl                                                    42      3-n-propyl-4-quinolyl                                                 43      3-n-butyl-4-quinolyl                                                  44      3-phenyl-4-quinolyl                                                   45      3-benzyl-4-quinolyl                                                   46      2-methyl-3-acetyl-4-quinolyl                                          47      2-phenyl-3-methoxy-4-quinolyl                                         48      2-methyl-3-cyano-4-quinolyl                                           49      6-methyl-4-quinolyl                                                   50      6-chloro-4-quinolyl                                                   51      7-chloro-4-quinolyl                                                   52      7-chloro-8-methyl-3-quinolyl                                          ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                         ##STR13##                                                                    Compounds of the formula Ib (R.sup.1 = OCH.sub.3, R.sup.2 = CH.sub.3 n =      1)                                                                            The configuration statement refers to the β-methoxyacrylate group.                                          mp. (°C.)                           No.  Het                     A     (isomer)                                   ______________________________________                                         53  2-pyridyl               S     oil (E)                                     54  6-methyl-2-pyridyl      O      79-80° C.                                                             (E)                                         55  6-methyl-2-pyridyl      S     oil (E)                                     56  6-ethyl-2-pyridyl       O                                                 57  6-ethyl-2-pyridyl       S                                                 58  6-n-propyl-2-pyridyl    O                                                 59  6-n-propyl-2-pyridyl    S                                                 60  6-isopropyl-2-pyridyl   O                                                 61  6-isopropyl-2-pyridyl   S                                                 62  6-n-butyl-2-pyridyl     O                                                 63  6-n-butyl-2-pyridyl     S                                                 64  6-tert.-butyl-2-pyridyl O                                                 65  6-tert.-butyl-2-pyridyl S                                                 66  6-n-pentyl-2-pyridyl    O                                                 67  6-n-pentyl-2-pyridyl    S                                                 68  6-n-hexyl-2-pyridyl     O                                                 69  6-n-hexyl-2-pyridyl     S                                                 70  6-phenyl-2-pyridyl      O                                                 71  6-phenyl-2-pyridyl      S                                                 72  6-benzyl-2-pyridyl      O                                                 73  6-benzyl-2-pyridyl      S                                                 74  6-trifluoromethyl-2-pyridyl                                                                           O                                                 75  6-trifluoromethyl-2-pyridyl                                                                           S                                                 76  6-methoxy-2-pyridyl     O                                                 77  6-methoxy-2-pyridyl     S                                                 78  6-chloro-2-pyridyl      O      88-89 (E)                                  79  6-chloro-2-pyridyl      S                                                 80  3,6-dimethyl-2-pyridyl  O                                                 81  3,6-dimethyl-2-pyridyl  S                                                 82  3,6-diethyl-2-pyridyl   O                                                 83  3,6-diethyl-2-pyridyl   S                                                 84  4,6-dimethyl-2-pyridyl  O                                                 85  4,6-dimethyl-2-pyridyl  S                                                 86  5,6-dimethyl-2-pyridyl  O                                                 87  5,6-dimethyl-2-pyridyl  S                                                 88  4-phenyl-6-methyl-2-pyridyl                                                                           O                                                 89  4-phenyl-6-methyl-2-pyridyl                                                                           S                                                 90  4,6-diphenyl-2-pyridyl  O                                                 91  4,6-diphenyl-2-pyridyl  S                                                 92  3,4-dichloro-6-methyl-2-pyridyl                                                                       O                                                 93  3,4-dichloro-6-methyl-2-pyridyl                                                                       S                                                 94  3,4,5-trichloro-6-phenyl-2-pyridyl                                                                    O                                                 95  3,4,5-trichloro-6-phenyl-2-pyridyl                                                                    S                                                 96  4-trifluoromethyl-6-methyl-2-pyridyl                                                                  O                                                 97  4-trifluoromethyl-6-methyl-2-pyridyl                                                                  S                                                 98  3-acetyl-4,6-dimethyl-2-pyridyl                                                                       O                                                 99  3-acetyl-4,6-dimethyl-2-pyridyl                                                                       S                                                100  3-cyano-6-methyl-2-pyridyl                                                                            O     135-137 (E)                                101  3-cyano-6-methyl-2-pyridyl                                                                            S                                                102  3-cyano-6-ethyl-2-pyridyl                                                                             O     177-178 (E)                                103  3-cyano-6-ethyl-2-pyridyl                                                                             S                                                104  3-cyano-6-n-propyl-2-pyridyl                                                                          O                                                105  3-cyano-6-n-propyl-2-pyridyl                                                                          S                                                106  3-cyano-6-isopropyl-2-pyridyl                                                                         O      97-98 (E)                                 107  3-cyano-6-isopropyl-2-pyridyl                                                                         S     117-118 (E)                                108  3-cyano-6-cyclopropyl-2-pyridyl                                                                       O     118-119 (E)                                109  3-cyano-6-cyclopropyl-2-pyridyl                                                                       S                                                110  3-cyano-6-n-butyl-2-pyridyl                                                                           O                                                111  3-cyano-6-n-butyl-2-pyridyl                                                                           S                                                112  3-cyano-6-tert.-butyl-2-pyridyl                                                                       O     124-125 (E)                                113  3-cyano-6-tert.-butyl-2-pyridyl                                                                       S                                                114  3-cyano-6-cyclohexyl-2-pyridyl                                                                        O                                                115  3-cyano-6-cyclohexyl-2-pyridyl                                                                        S                                                116  3-cyano-6-phenyl-2-pyridyl                                                                            O                                                117  3-cyano-6-phenyl-2-pyridyl                                                                            S                                                118  3-methyloxycarbonyl-6-isopropyl-2-pyridyl                                                             O                                                119  3-methyloxycarbonyl-6-isopropyl-2-pyridyl                                                             S                                                120  3-ethyloxycarbonyl-6-isopropyl-2-pyridyl                                                              O     oil (E)                                    121  3-ethyloxycarbonyl-6-isopropyl-2-pyridyl                                                              S                                                122  3-cyano-4,6-dimethyl-2-pyridyl                                                                        O     122-124 (E)                                123  3-cyano-4,6-dimethyl-2-pyridyl                                                                        S                                                124  3,5,6-trichloro-2-pyridyl                                                                             O                                                125  3,5,6-trichloro-2-pyridyl                                                                             S                                                126  5-trifluoromethyl-2-pyridyl                                                                           O                                                127  5-trifluoromethyl-2-pyridyl                                                                           S      62-63 (E)                                 128  3-chloro-5-trifluoromethyl-2-pyridyl                                                                  O                                                129  3-chloro-5-trifluoromethyl-2-pyridyl                                                                  S     oil (E)                                    130  2-quinolyl              O                                                131  2-quinolyl              S     oil (E)                                    132  3-methyl-2-quinolyl     O                                                133  3-methyl-2-quinolyl     S                                                134  4-methyl-2-quinolyl     O     oil (E)                                    135  4-methyl-2-quinolyl     S                                                136  4-ethyl-2-quinolyl      O                                                137  4-ethyl-2-quinolyl      S                                                138  4-phenyl-2-quinolyl     O                                                139  4-phenyl-2-quinolyl     S                                                140  6-methyl-2-quinolyl     O                                                141  6-methyl-2-quinolyl     S                                                142  6-chloro-2-quinolyl     O                                                143  6-chloro-2-quinolyl     S                                                144  8-methyl-2-quinolyl     O                                                145  8-methyl-2-quinolyl     S                                                146  8-chloro-2-quinolyl     O                                                147  8-chloro-2-quinolyl     S                                                148  4-ethoxycarbonyl-2-quinolyl                                                                           O                                                149  4-ethoxycarbonyl-2-quinolyl                                                                           S                                                150  3,4-dimethyl-2-quinolyl O                                                151  3,4-dimethyl-2-quinolyl S                                                152  4-methyl-8-methoxy-2-quinolyl                                                                         O                                                153  4-methyl-8-methoxy-2-quinolyl                                                                         S                                                154  4-phenyl-8-ethoxy-2-quinolyl                                                                          O                                                155  4-phenyl-8-ethoxy-2-quinolyl                                                                          S                                                156  4-methyl-8-chloro-2-quinolyl                                                                          O                                                157  4-methyl-8-chloro-2-quinolyl                                                                          S                                                158  4-methyl-8-fluoro-2-quinolyl                                                                          O                                                159  4-methyl-8-fluoro-2-quinolyl                                                                          S                                                160  4-quinolyl              O                                                161  4-quinolyl              S                                                162  2-methyl-4-quinolyl     O     129-130 (E)                                163  2-methyl-4-quinolyl     S                                                164  2-trichloromethyl-4-quinolyl                                                                          O                                                165  2-trichloromethyl-4-quinolyl                                                                          S                                                166  2-trifluoromethyl-4-quinolyl                                                                          O                                                167  2-trifluoromethyl-4-quinolyl                                                                          S                                                168  2-isopropyl-4-quinolyl  O                                                169  2-isopropyl-4-quinolyl  S                                                170  2-n-pentyl-4-quinolyl   O                                                171  2-n-pentyl-4-quinolyl   S                                                172  2-phenyl-4-quinolyl     O                                                173  2-phenyl-4-quinolyl     S                                                174  2-methoxycarbonyl-4-quinolyl                                                                          O                                                175  2-methoxycarbonyl-4-quinolyl                                                                          S                                                176  2,6-dimethyl-4-quinolyl O                                                177  2,6-dimethyl-4-quinolyl S                                                178  2-methyl-6-chloro-4-quinolyl                                                                          O                                                179  2-methyl-6-chloro-4-quinolyl                                                                          S                                                180  2-methyl-6-fluoro-4-quinolyl                                                                          O                                                181  2-methyl-6-fluoro-4-quinolyl                                                                          S                                                182  8-quinolyl              O                                                183  8-quinolyl              S                                                184  2-methyl-8-quinolyl     O     oil (E)                                    185  2-methyl-8-quinolyl     S                                                186  5,7-dichloro-8-quinolyl O     106-107 (E)                                187  5,7-dichloro-8-quinolyl S                                                188  4,6-dimethyl-2-pyrimidinyl                                                                            O                                                189  4,6-dimethyl-2-pyrimidinyl                                                                            S     133-134 (E)                                190  4-trifluoromethyl-2-pyrimidinyl                                                                       O                                                191  4-trifluoromethyl-2-pyrimidinyl                                                                       S      85-86 (E)                                 192  4,5,6-trimethyl-2-pyrimidinyl                                                                         O                                                193  4,5,6-trimethyl-2-pyrimidinyl                                                                         S                                                194  4-benzyl-6-methyl-2-pyrimidinyl                                                                       O                                                195  4-benzyl-6-methyl-2-pyrimidinyl                                                                       S                                                196  4-methyl-6-phenyl-2-pyrimidinyl                                                                       O                                                197  4-methyl-6-phenyl-2-pyrimidinyl                                                                       S                                                198  4,6-dimethyl-5-chloro-2-pyrimidinyl                                                                   O                                                199  4,6-dimethyl-5-chloro-2-pyrimidinyl                                                                   S                                                200  2,6-dimethyl-4-pyrimidinyl                                                                            O                                                201  2,6-dimethyl-4-pyrimidinyl                                                                            S                                                202  2,6-bis-(trifluoromethyl)-4-pyrimidinyl                                                               O      57-58 (E)                                 203  2,6-bis-(trifluoromethyl)-4-pyrimidinyl                                                               S                                                204  2-chloromethyl-6-methyl-4-pyrimidinyl                                                                 O                                                205  2-chloromethyl-6-methyl-4-pyrimidinyl                                                                 S                                                206  2-methyl-6-chloromethyl-4-pyrimidinyl                                                                 O                                                207  2-methyl-6-chloromethyl-4-pyrimidinyl                                                                 S                                                208  2-isopropyl-6-methyl-4-pyrimidinyl                                                                    O                                                209  2-isopropyl-6-methyl-4-pyrimidinyl                                                                    S                                                210  2-isopropyl-6-chloromethyl-4-pyrimidinyl                                                              O                                                211  2-isopropyl-6-chloromethyl-4-pyrimidinyl                                                              S                                                212  2-cyclopropyl-6-chloromethyl-4-                                                                       O                                                     pyrimidinyl                                                              213  2-cyclopropyl-6-chloromethyl-4-                                                                       S                                                     pyrimidinyl                                                              214  2-cyclopropyl-6-methyl-4-pyrimidinyl                                                                  O                                                215  2-cyclopropyl-6-methyl-4-pyrimidinyl                                                                  S                                                216  2-methyl-6-methoxymethyl-4-pyrimidinyl                                                                O                                                217  2-methyl-6-methoxymethyl-4-pyrimidinyl                                                                S                                                218  2-isopropyl-6-methoxymethyl-4-                                                                        O                                                     pyrimidinyl                                                              219  2-isopropyl-6-methoxymethyl-4-                                                                        S                                                     pyrimidinyl                                                              220  2-phenyl-4-pyrimidinyl  O                                                221  2-phenyl-4-pyrimidinyl  S                                                222  2,5-dimethyl-4-pyrimidinyl                                                                            O                                                223  2,5-dimethyl-4-pyrimidinyl                                                                            S                                                224  2-methylthio-6-trifluoromethyl-4-                                                                     O     111-112 (E)                                     pyrimidinyl                                                              225  2-methylthio-6-trifluoromethyl-4-                                                                     S                                                     pyrimidinyl                                                              226  2-methylthio-5-chloro-6-trifluoromethyl-4-                                                            O     oil (E)                                         pyrimidinyl                                                              227  2-methylthio-5-chloro-6-trifluoromethyl-4-                                                            S                                                     pyrimidinyl                                                              228  2-methylthio-5-n-octyl-6-methyl-4-                                                                    O                                                     pyrimidinyl                                                              229  2-methylthio-5-n-octyl-6-methyl-4-                                                                    S                                                     pyrimidinyl                                                              230  2-methyl-6-trifluoromethyl-4-pyrimidinyl                                                              O                                                231  2-methyl-6-trifluoromethyl-4-pyrimidinyl                                                              S     oil (E)                                    232  2-n-propyl-6-trifluoromethyl-4-pyrimidinyl                                                            O      81-82 (E)                                 233  2-n-propyl-6-trifluoromethyl-4-pyrimidinyl                                                            S                                                234  2-isopropyl-6-trifluoromethyl-4-                                                                      O                                                     pyrimidinyl                                                              235  2-isopropyl-6-trifluoromethyl-4-                                                                      S                                                     pyrimidinyl                                                              236  2-tert.-butyl-6-trifluoromethyl-4-                                                                    O                                                     pyrimidinyl                                                              237  2-tert.-butyl-6-trifluoromethyl-4-                                                                    S                                                     pyrimidinyl                                                              238  2-methyl-5-chloro-6-trifluoromethyl-4-                                                                O                                                     pyrimidinyl                                                              239  2-methyl-5-chloro-6-trifluoromethyl-4-                                                                S                                                     pyrimidinyl                                                              240  2-n-propyl-5-chloro-6-trifluoromethyl-4-                                                              O                                                     pyrimidinyl                                                              241  2-n-propyl-5-chloro-6-trifluoromethyl-4-                                                              S                                                     pyrimidinyl                                                              242  2-isopropyl-5-chloro-6-trifluoromethyl-4-                                                             O                                                     pyrimidinyl                                                              243  2-isopropyl-5-chloro-6-trifluoromethyl-4-                                                             S                                                     pyrimidinyl                                                              244  2-tert.-butyl-5-chloro-6-trifluoromethyl-4-                                                           O                                                     pyrimidinyl                                                              245  2-tert.-butyl-5-chloro-6-trifluoromethyl-4-                                                           S                                                     pyrimidinyl                                                              246  2-pyrimidinyl           S     oil (E)                                    255  3-ethyloxycarbonyl-6-cyclopropyl-2-                                                                   O     oil (E)                                         pyridyl                                                                  256  3-trifluoromethyl-6-isopropyl-2-pyridyl                                                               O     oil (E)                                    257  2-phenyl-6-trifluoromethyl-4-pyrimidinyl                                                              O     109-110 (E)                                258  2-methylthio-6-difluoromethyl-4-                                                                      O      77-78 (E)                                      pyrimidinyl                                                              ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR14##                                                                    Compounds of the formula Ic (n = O, R.sup.1 = OCH.sub.3, R.sup.2 =            CH.sub.3)                                                                     The configuration statement refers to the β-methoxyacrylate              group.                                                                                                       mp. (°C.)                               No.  Het                       (isomer)                                       ______________________________________                                        247  2-pyridon-1-yl            103-104 (E)                                    248  6-methyl-2-pyridon-1-yl   149-150 (E)                                    249  3-cyano-6-methyl-2-pyridon-1-yl                                                                         181-183 (E)                                    250  4-pyridon-1-yl            144-145 (E)                                    251  2-pyrimidinon-1-yl        oil (E)                                        252  4-pyrimidinon-1-yl         85-86 (E)                                     253  6-pyrimidinon-1-yl         95-96 (E)                                     254  2-n-propyl-4-trifluoromethyl-6-pyrimidinon-                                                              90-92 (E)                                          1-yl                                                                     259  4-trifluoromethyl-2-pyrimidon-1-yl                                                                      219-220 (E)                                    260  5-trifluoromethyl-2-pyridon-1-yl                                                                        oil (E)                                        261  3-chloro-5-trifluoromethyl-2-pyridon-1-yl                                                               113-114 (E)                                    ______________________________________                                    

Table 4

NMR data for selected compounds from Tables 1, 2 and 3. The chemicalshift (δ) is stated in ppm relative to tetramethylsilane. The solventwas CDCl₃.

Compound no. 1

3.61 (s, 3H); 3.79 (s, 3H); 5.36 (s, 2H); 7.16-7.56 (m, 5H); 7.60 (s,1H); 7.80 (t, 1H); 8.08 (d, 1H); 8,68 (d, 1H).

Compound no. 13

3.63 (s, 3H); 3,78 (s, 3H); 5.32 (s, 2H); 7.17-7.55 (m, 5H); 7.60 (s,1H); 8,28 (d, 1H); 8.76 (d, 1H); 9.21 (s, 1H).

Compound no. 32

3.64 (s, 3H); 3.80 (s, 3H); 5.37 (s, 2H); 7.21-7.65 (m, 5H); 7.61 (s,1H); 7.84 (t, 1H); 7.95 (d, 1H); 8.17 (d, 1H); 8.85 (s, 1H); 9.45 (s,1H).

Compound no. 53

3.67 (s, 3H); 3.75 (s, 3H); 4.35 (s, 2H); 6.90-7.53 (m, 7H); 7.56 (s,1H); 8.40 (d, 1H).

Compound no. 54

2.43 (s, 3H); 3.68 (s, 3H); 3.77 (s, 3H); 5.27 (s, 2H); 6.50 (d, 1H);6.68 (d, 1H); 7.15-7.55 (m, 5H); 7.60 (s, 1H).

Compound no. 78

3.70 (s, 3H); 3.82 (s, 3H); 5.28 (s, 2H); 6.62 (d, 1H); 6.88 (d, 1H);7.15-7.55 (m, 5H); 7.58 (s, 1H).

Table 4: (contd.)

Compound no. 100

2.50 (s, 3H); 3.73 (s, 3H); 3.85 (s, 3H); 5.42 (s, 2H); 6.80 (d, 1H);7.18-7.69 (m, 4H); 7.65 (s, 1H); 7.74 (d, 1H).

Compound no. 102

1.28 (t, 3H); 2.75 (q, 2H); 3.72 (s, 3H); 3.84 (s, 3H); 5.43 (s, 2H);6.78 (d, 1H); 7.16-7.64 (m, 4H); 7.60 (s, 1H); 7.73 (d, 1H).

Compound no. 106

1.26 (d, 6H); 2.98 (quin., 1H); 3.72 (s, 3H); 3.84 (s, 3H); 5.44 (s,2H); 6.79 (d, 1H); 7.18-7.67 (m, 4H); 7.63 (s, 1H); 7.74 (d, 1H).

Compound no. 108

1.05 (m, 4H); 1.96 (m, 1H); 3.72 (s, 3H); 3.85 (s, 3H); 5.35 (s, 2H);6.83 (d, 1H); 7.16-7.55 (m, 4H); 7.63 (s, 1H); 7.65 (d, 1H).

Compound no. 122

2.42 (s, 3H); 2.43 (s, 3H); 3.71 (s, 3H); 3.86 (s, 3H); 5.38 (s, 2H);6.67 (s, 1H); 7.14-7.63 (m, 4H); 7.61 (s, 1H).

Compound no. 131

3.68 (s, 3H); 3.75 (s, 3H); 4.60 (s, 2H); 7.08-7.65 (m, 8H); 7.53 (s,1H); 7.77 (d, 1H); 7.93 (d, 1H).

Compound no. 134

2.60 (s, 3H); 3.68 (s, 3H); 3.79 (s, 3H); 5.43 (s, 2H); 6.75 (s, 1H);7.13-7.87 (m, 8H); 7.57 (m, 1H).

Compound no. 162

2.65 (s, 3H); 3.69 (s, 3H); 3.80 (s, 3H); 5.16 (s, 2H); 6.57 (s, 1H);7.20-7.67 (m, 6H); 7.57 (s, 1H); 7.93 (s, 1H); 8.19 (s, 1H).

Compound no. 184

2.80 (s, 3H); 3.72 (s, 3H); 3.79 (s, 3H); 5.39 (s, 2H); 6.85 (d, 1H);7.16-7.28 (m, 6H); 7.64 (m, 2H); 7.95 (d, 1H).

Compound no. 186

3.68 (s, 3H); 3.79 (s 3H); 5.42 (s, 2H); 7.16-7.60 (m 4H); 7.50 (s 1H);7.65 (s, 1H); 8.04 (d, 1H); 8.53 (d, 1H); 9.02 (d, 1H).

Compound no. 202

3.68 (s, 3H); 3.83 (s, 3H); 5.50 (s, 2H); 7.16 (s, 1H); 7.20-7.58 (m,4H); 7.60 (s, 1H).

Compound no. 224

2.55 (s, 3H); 3.69 (s, 3H); 3.81 (s, 3H); 5.40 (s, 2H); 6.68 (s, 1H);7.29-7.54 (m, 4H); 7.60 (s, 1H).

Compound no. 226

2.57 (s, 3H); 3.72 (s, 3H); 3.84 (s, 3H); 5.48 (s, 2H); 7.20-7.60 (m,4H); 7.62 (s, 1H).

Compound no. 232

1.01 (t, 3H); 1.87 (sext., 2H); 2.90 (t, 2H); 3.70 (s, 3H); 3.81 (s,3H); 5.40 (s, 2H); 6.86 (s, 1H); 7.20-7.58 (m, 4H); 7.60 (s, 1H).

Compound no. 246

3.70 (s, 3H); 3.83 (s, 3H); 4.34 (s, 2H); 6.98 (t, 1H); 7.12-7.58 (m,4H); 7.60 (s, 1H); 8.52 (d, 2H).

Compound no. 247

3.64 (s, 3H); 3.84 (s, 3H); 5.08 (s, broad, 2H); 6.05 (t, 1H); 6.56 (d,1H); 7.07-7.35 (m, 6H); 7.57 (s, 1H).

Compound no. 249

2.20 (s, 3H); 3.71 (s, 3H); 3.88 (s, 3H); 5.26 (s, broad, 2H); 6.11 (d,1H); 6.81 (d, 1H); 7.15-7.70 (m, 4H); 7.65 (s, 1H).

Compound no. 250

3.56 (s, 3H); 3.80 (s, 3H); 4.87 (s, 2H); 6.05 (d, 2H); 7.10-7.35 (m,4H); 7.50 (d, 2H); 7.68 (s, 1H).

Compound no. 251

3.67 (s, 3H); 3.85 (s, 3H); 5.03 (s, 2H); 6.22 (m, 1H); 7.21-7.50 (m,5H); 7.60 (s, 1H); 8.65 (m, 1H).

Compound no. 252

3.53 (s, 3H); 3.79 (s, 3H); 4.87 (s, 2H); 5.96 (d, 1H); 7.09-7.48 (m,5H); 7.68 (s, 1H); 8.27 (d, 1H).

Compound no. 253

3.64 (s, 3H); 3.80 (s, 3H); 5.03 (s, broad, 2H); 6.44 (d, 1H); 7.17-7.39(m, 4H); 7.59 (s, 1H); 7.84 (d, 1H); 7.92 (s, 1H).

Compound no. 254

0.88 (t, 3H); 1.68 (sext., 2H); 2.49 (t, 2H); 3.72 (s, 3H); 3.91 (s,3H); 5.22 (s, broad, 2H); 6.80 (s, 1H); 6.87-7.33 (m, 4H); 7.68 (s, 1H).

Generally speaking, the novel compounds are extremely effective on abroad spectrum of phytopathogenic fungi, in particular those from theAscomycetes and Basidiomycetes classes. Some of them have a systemicaction and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The compounds are applied by spraying or dusting the plants with theactive ingredients, or treating the seeds of the plants with the activeingredients. They may be applied before or after infection of the plantsor seeds by the fungi.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin, sulfitewaste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient. The application rates arefrom 0.02 to 3 kg or more of active ingredient per hectare, depending onthe type of effect desired. The novel compounds may also be used forprotecting materials, for example against Paecilomyces variotii.

The agents and the ready-to-use formulations prepared from them, such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 53 is mixed with 10 parts byweight of N-methyl-α-pyrrolidone. A mixture is obtained which issuitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 131 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into water and uniformly distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of compound no. 162 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water andfinely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 246 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into water and uniformlydistributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 53 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill. By uniformly distributing themixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 131 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 162 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 40 parts by weight of compound no. 246 is intimately mixed with 10parts of the sodium salt of a phenolsulfonic acid-urea-formaldehydecondensate, 2 parts of silica gel and 48 parts of water to give a stableaqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 53 is intimately mixed with 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil. A stable oilydispersion is obtained.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in an increase in thefungicidal spectrum.

The following list of fungicides with which the novel compounds may becombined is intended to illustrate possible combinations but not toimpose any restrictions.

Examples of fungicides which may be combined with the novel compoundsare:

sulfur,

dithiocarbamates and their derivatives, such as

ferric dimethyldithiocarbamate,

zinc dimethyldithiocarbamate,

zinc ethylenebisdithiocarbamate,

manganese ethylenebisdithiocarbamate,

manganese zinc ethylenediaminebisdithiocarbamate,

tetramethylthiuram disulfides,

ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,

ammonia complex of zinc N,N'-propylenebisdithiocarbamate,

zinc N,N'-propylenebisdithiocarbamate and

N,N'-polypropylenebis(thiocarbamyl) disulfide;

nitro derivatives, such as

dinitro(1-methylheptyl)-phenyl crotonate,

2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and diisopropyl5-nitroisophthalate;

heterocyclic substances, such as

2-heptadecylimidazol-2-yl acetate,

2,4-dichloro-6-(o-chloroanilino)-s-triazine,

O,O-diethyl phthalimidophosphonothioate,

5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone,

2-thio-1,3-dithio[4,5-b]quinoxaline,

methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,

2-methoxycarbonylaminobenzimidazole,

2-(fur-2-yl)-benzimidazole,

2-(thiazol-4-yl)benzimidazole,

N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,

N-trichloromethylthiotetrahydrophthalimide,

N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-thiocyanatomethylthiobenzothiazole,

1,4-dichloro-2,5-dimethoxybenzene,

4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,

2-thiopyridine 1-oxide,

8-hydroxyquinoline and its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,

2-methylfuran-3-carboxanilide,

2,5-dimethylfuran-3-carboxanilide,

2,4,5-trimethylfuran-3-carboxanilide,

2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,

N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,

2-methylbenzanilide,

2-iodobenzanilide,

N-formyl-N-morpholine-2,2,2-trichloroethylacetal,

piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine,

1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole

1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,

1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,

α-(2-chlorophenyl) -α-(4-chlorophenyl)-5-pyrimidinemethanol,

5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,

bis-(p-chlorophenyl)-3-pyridinemethanol,

1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,

1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,

and various fungicides, such as

dodecylguanidine acetate,

3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide,

hexachlorobenzene,

DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate,

methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanate,

N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,

methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,

5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,

3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,

3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,

N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,

2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,

1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,

2,4-difluoro-α-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,

N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,and

1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.

USE EXAMPLES

The following prior art compounds were used for comparison purposes:methyl α-(2-benzyloxyphenyl)-β-methoxyacrylate (A) disclosed in DE3,519,282; methyl α-(2-phenoxymethylphenyl)-β-methoxyacrylate (B)disclosed in DE 3,545,319; methylα-2-(2-pyridyl)-oxyphenyl-β-methoxyacrylate (D) disclosed in EP 178,826;and methyl α-2-(6-methylpyridyl)oxyphenyl-β-methoxyacrylate (C)disclosed in EP 242,081.

USE EXAMPLE 1 Action on Pseudocercosporella herpotrichoides

Wheat plants of the "Fruhgold" variety were sprayed to runoff at theone-leaf stage with aqueous formulations containing (dry basis) 80% (wt%) of active ingredient and 20% of emulsifier. After 24 hours the plantswere inoculated with a Spore suspension of Pseudocercosporellaherpotrichoides. For optimum development of the plant disease the plantswere then set up for one week in a climatic cabinet at from 16° to 18°C. and a relative humidity in excess of 95%. The plants were thencultivated for a further two weeks in the greenhouse at 15° to 17° C.The spread of the disease was then assessed on the lower portion of theplant stem.

The results show that compounds nos. 53, 100, 131, 162, 189 and 246,applied as 0.1% spray liquors, had a better fungicidal action (90%) thanprior art active ingredients A and B (70%).

USE EXAMPLE 2 Action on Wheat Brown Rust

Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dustedwith spores of brown rust (Puccinia recondita). The pots were thenplaced for 24 hours at 20° to 22° C. in a high-humidity (90-95%)chamber. During this period the spores germinated and the germ tubespenetrated the leaf tissue. The infected plants were then sprayed torunoff with aqueous liquors containing (dry basis) 80% of activeingredient and 20% of emulsifier. After the sprayed-on layer had dried,the plants were set up in the greenhouse at 20° to 22° C. and a relativehumidity of 65 to 70%. The extent of rust fungus spread on the leaveswas assessed after 8 days.

The results show that compounds nos. 54, 78, 127, 129 and 256, appliedas 0.0015% spray liquors, had a better fungicidal action (97%) thanprior art compounds A, B, C and D (35%).

USE EXAMPLE 3 Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed withaqueous suspensions containing (dr) basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 8 days in the greenhouse.

Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 48 hours in a watervapor-saturated chamber at 24° C. and then in a greenhouse for 5 days atfrom 20° to 30° C. To accelerate and intensify the sporangiophoredischarge, the plants were then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results show that compounds nos. 78, 100, 129, 191, 232 and 256,applied as 0.006% spray liquors, had a better fungicidal action (100%)than prior art active ingredients C and D (70%).

We claim:
 1. A compound selected from the group consisting of a compoundof formula I ##STR15## wherein Het is a member selected from the groupconsisting of 2-quinolyl; 4-methyl-2-quinolyl;3-chloro-5-trifluoromethyl-2-pyridyl;2-methyl-6-trifluoromethyl-4-pyrimidinyl;4-trifluoromethyl-2-pyrimidinyl; 6-methyl-2-pyridyl; and6-isopropyl-2-pyridyl; A is sulfur; R¹ is methoxy; R² is methyl; and nis 1; and its plant-tolerated acid addition salts, metal complexes, andN-oxides.
 2. A method for combating fungi, comprising contacting thefungi, or the materials, plants, seed or soil to be protected againstfungus attack, with a fungicidally effective amount of a compound ofclaim
 1. 3. A fungicidal composition comprising an inert carrier and afungicidally effective amount of a compound of claim
 1. 4. A compoundaccording to claim 1 wherein Het is 2-quinolyl, R¹ is methoxy, and R² ismethyl.
 5. A compound according to claim 1 wherein Het is4-methyl-2-quinolyl, R¹ is methoxy, and R² is methyl.
 6. A compoundaccording to claim 1 wherein Het is3-chloro-5-trifluoromethyl-2-pyridyl, R¹ is methoxy, and R² is methyl.7. A compound according to claim 1 wherein Het is2-methyl-6-trifluoromethyl-4-pyrimidinyl, R¹ is methoxy, and R² ismethyl.
 8. A compound according to claim 1 wherein Het is4-trifluoromethyl-2-pyrimidinyl, R¹ is methoxy, and R² is methyl.
 9. Acompound according to claim 1 wherein Het methyl-2-pyridyl, R¹ ismethoxy, and R² is methyl.
 10. A compound according to claim 1 whereinHet is isopropyl-2-pyridyl, R¹ is methoxy, and R² is methyl.